THERMODYNAMICS and KINETICS 534
SPRING 1999
Syllabus for the kinetics part of the course
A brief six week introduction to chemical kinetics

Instructor - Professor James Schlegel
Text ­ Chemical Kinetics by Kenneth A. Connors, VCH Publishers,
Inc.
I am told that the book store will have this book by March 22, 1999
Now I am told that this book will not be available until late April - TOO
LATEI will copy the problems for you and my notes should be sufficient.
You can use most any Physical Chemistry text to get the material.
A good one is Physical Chemistry by Atkins (the publisher is Freeman).
There is another book I used two years ago by James Espenson but it is
very expensive for its size. McGraw-Hill is the publisher and the
title is Chemical Kinetics and Reaction Mechanisms.

B. Methods of establishing a rate law and
evaluation of rate constants Integrated rate equations
Infinite-time method: use a physical property when this property is directly
proportional to concentration
Guggenheim method
Time-lag method (Kezdy-Swinbourne)

Differential rate equations
Intial rate method - order with respect to concentration
Continous slope method - order with respect to time

Isolation method - pseudo
(or observed) rate constants

Competition methods (Parallel
reactions)

The steady-state approximation
and the pre-equilibrium approximation

Consecutive reactions and
concurrent reactions

Reversible first order reactions
(compare treatment with that for relaxation kinetics)

A --> P
-d[A]/dt = d[P]/dt = k[A]n
where n = order
First order processes are most often encountered n = 1

Can use [A] = conc. of A at any time or use Ao - x
where x is the extent of the reaction
-dA/dt = - d(Ao
- x )/dt = dx/dt = k[A] = k(Ao - x )
-d[A]/dt = k[A] or -d(Ao
- x)/dt = k(Ao - x) get the same result

Different ways topresent the data
1. Graph
2. Tabulate
3. Linear regression on computer or calculator
Can do a general regression analysis (non-linear)

Infinite time method
For first order, can plot
ln(Poo-P) to get a straight line with slope equal
to -k as long as the property, P, is directly
proportional to concentration
Spectroscopy |Aoo-A|
Dilatometry |Voo-V|
Conductance |Loo-L|
= |1/Roo - 1/R|
Polarimetry |aoo-a|
and in general. |Poo- P| a
concentration of reactant in limiting concentration

Initial rate method: Obtain initial rate at
several different concentrations and from a
plot of log(R) vs log[A] obtain the order - refer
to this as the order with respect to concentration

Continuous slope method: From a plot of [A]
vs time obtain the slope at various times (which identifies
a concentration, [A], on this curve and a plot of
log(R) (which equals log(d[A]/dt)) vs log[A] yields the
oder, n - refer tothis as the order with respect
to concentration. If the order from the initial rate method is
not the same as the order from the continuous slope
method, then the reaction is autocatalytic or autoinhibitory.
If ntime>nconc then it is autocatalytic

Reversible reactions (also the treatment of data from perturbation
or relaxation techniques)